Paraquat (PQ) as a widely used non-selective herbicides has gained attention in agricultural residue detection and food safety. Herein, a novel quantitative analysis approach for PQ was proposed based on a novel kind of aggregation-induced emission electrochemiluminescence (AIECL) emitters, tetraphenylethylene-luminol (TPE-L) with a small molecule-induced multiple catalytic hairpin assembly (CHA) amplification strategy, the competitive immune reaction and CRISPR/Cas12a system. The target molecule PQ is introduced into a signal cycle, and auxiliary sensitization cycles are constructed by virtue of the cleavage characteristics of the CRISPR/Cas12a system, which realized the multiple utilization of the target by using both cis- and trans-cleavage activities. In addition, the new multiple CHA amplification strategy was attributed to cross-catalytic hairpin assembly caused by the products of the CHA cycle as the initiator chain of the next CHA cycle, realizing the efficient utilization of cyclic products and producing high-efficiency signal amplification. Thus, the ECL biosensor for ultrasensitive analysis of PQ was successfully constructed with a limit of detection of 0.7 pg/mL. Importantly, it could be easily-extended to other small molecules simply by replacing paired antibodies, providing prospects in agricultural residue detection, food safety and related medical applications.

Cancer cell-derived exosomes serve as crucial biomarkers for thyroid cancer, which has emerged as the fourth most prevalent malignancy among urban Chinese women. However, achieving high sensitivity and precision in their in vitro detection remains challenging. Traditional diagnostic methods for thyroid cancer, including tumor-associated marker detection and imaging examinations, are limited by high costs and poor sensitivity. Among various biomarkers, miRNA-146b-5p has been identified as a key marker associated with the progression of thyroid cancer, which poses a formidable challenge in achieving exquisite sensitivity and precision in vitro detection. Herein, we developed an electrochemiluminescence (ECL) biosensor for the sensitive detection of the thyroid cancer marker miRNA-146b-5p, based on Zr-PTC and combining an ECL resonance energy transfer (ECL-RET) system with a toehold-mediated strand displacement reaction (TSDR) signal amplification strategy. Initially, Zr-PTC was employed as the ECL signal label, with miRNA-146b-5p as the model target to initiate the TSDR cycle, resulting in the release of the output chain (output). The output chain assisted the unfolding of hairpin DNA H1 (H1), which exposed its complementary sequence that hybridizes with the ECL quenching material (AgCl NPs-S1), thereby resulting in a significant reduction of the ECL signal. The combination of target cyclic amplification and metal-organic framework-based signal labeling significantly enhanced the sensitivity of the proposed biosensor, achieving limit of detection (LOD) for miRNA-146b-5p as low as 0.69 fM (S/N = 3). This innovative analytical methodology presents a promising strategy for detecting exosomal RNA biomarkers associated with thyroid malignancies. The integration of RET system with TSDR signal amplification not only enhanced detection sensitivity but also demonstrated robust reproducibility and stability, offering broad applicability for sensitive nucleic acid detection in human serum samples.

A facile electrochemiluminescence (ECL) immunosensor for the sensitive detection of the prostate-specific antigen (PSA) was constructed based on a co-reactant modulating strategy using a Cu2+-modified NH2-metal-organic framework (NMOF@Cu2+) nanoprobe as a modulating unit. The biconical NMOF@Cu2+ nanoprobe possessed a large number of carboxyl groups, which could be labeled by the target PSA to form a PSA-NMOF@Cu2+ conjugate. Moreover, the nanoprobe could consume K3[Fe(CN)6], resulting in a lower signal of the luminol-K3[Fe(CN)6] ECL system. The bioassay was executed in a split-type mode. First, the competitive immunological recognition reaction with the PSA-NMOF@Cu2+ conjugate as the signal probe was performed in an antibody labeled 96-well plate. In the presence of the target PSA, the PSA competes with the PSA-NMOF@Cu2+ conjugate for immobilization, which determines the amount of PSA-NMOF@Cu2+ conjugates immobilized in the plate and results in different amounts of prefilled K3[Fe(CN)6] being consumed. Subsequently, the above solution was transferred to the detection cell for ECL testing, whereby the ECL signal from the luminol-K3[Fe(CN)6] system reflected the content of the PSA. The developed ECL immunosensor showed high sensitivity for the PSA with a linear response range of 1.0 pg mL-1-10 ng mL-1 and a detection limit of 0.5 pg mL-1. Moreover, the applicability of the present method was demonstrated by the determination of the PSA in human serum.

Structurally driven properties of hybrid materials are a fascinating feature of metal-organic framework (MOF) materials that can serve as hosts for various responsive dye molecules. In particular, the formation of aggregates and the related shift of the emission of fluorophors can be tuned as a function of pore confinement. In this work, the fluorosolvatochromic methylated photoacid tris(2,2,2-trifluoroethyl) 8-methoxypyrene-1,3,6-trisulfonate (MePhos) and the free photoacid tris(2,2,2-trifluoroethyl) 8-hydroxypyrene-1,3,6-trisulfonate (Phos) were inserted into various MOF scaffolds, and the resulting emission properties were found to be far beyond the observed red shifts for polar solvents such as methanol or ethanol. Instead of the modulation of the band gap by the local environment given by the physicochemical properties of the MOF pores, there is aggregation of the MePhos molecules depending on the MOF structure, leading either to H- or t o J-like character.

The potential hazards of bisphenol A (BPA) to the environment have become a global concern. Herein, 2D Zn-based metal-organic framework nanosheet (2D Zn-MOF) and MnCO3 nanocomposite (Zn-MOF-MnCO3), an efficient electrochemiluminescence (ECL) probe was first synthesized and constructed for trace detection of BPA. Owing to the elimination of the aggregation-induced quenching (ACQ) effect of polycyclic aromatic hydrocarbons (PAHs), the leaf-like Zn-MOF exhibited a satisfactory ECL signal. The MnCO3, which has excellent biocompatibility, showed excellent ECL efficiency in the presence of K2S2O8. With the covalent binding of Zn-MOF and MnCO3, we demonstrated that the ECL intensity and stability of Zn-MOF-MnCO3 improved significantly. In addition, the inner filter effect (IFE) of Fe3O4-NH2 NPs toward Zn-MOF-MnCO3 had been confirmed to be the ECL quenching mechanism. Based on above strategies, the proposed ECL-IFE biosensor exhibited a trace detection ability of BPA in a wide linear range (10 fM ∼ 10 μM) with a low detection limit (4.2 fM). Further in-depth study confirmed the excellent repeatability, selectivity, and stability of sensors, which provided a fresh sensing platform for trace detection of BPA in the environment.

Metal-organic frameworks (MOFs) are a class of materials composed of coordinative interactions between metal ions and organic linkers, encompassing two-dimensional (2D), and three-dimensional (3D) architectures. Metal-organic cages (MOCs), a special case of these species, are discrete molecular "capsules" with zero-dimensional (0D) structures. Over the last two decades, MOFs and MOCs composed of organic perylene (P) and perylene diimide (PDI) linkers have gained much attention due to their versatile properties, which can be further enhanced after incorporation into frameworks. This minireview highlights recent progress in the construction and application of P/PDI-based coordination framework materials. The text offers an overview of the synthesis of P/PDI organic linkers, proceeds to their integration into coordination frameworks of different dimensionalities - 2D and 3D MOFs, and 0D MOCs, and then explores potential applications. These include sensing, photocatalysis, electrochemical devices and photothermal conversion and focus on the apparent structure-property relationships. Finally, the challenges and future prospects of P/PDI-derived coordination frameworks will be addressed.

Serum amyloid A (SAA) is a key biomarker for diagnosing inflammatory responses in diseases like influenza and COVID-19. An electrochemiluminescence (ECL) biosensor has been constructed for signal enhancement in SAA detection by encapsulating 4,4',4″,4‴-(1,3,6,8-pyrenetetrayl) tetrakis-benzoic acid (TBAPy) into liposomes. Such biomimetic encapsulation shields the biologically important membrane to avoid aggregation of TBAPy and prevents quenching. It would enhance the ECL signal's stability and intensity, resulting in a 5-fold signal increase with a relative standard deviation (RSD) of 1.71%. The biosensor has shown very good specificity and sensitivity toward SAA detection. The estimated detection limit is 0.188 pg/mL. This innovative approach integrates biomimicry with ECL technology and represents a leap in developing the next generation of diagnostic tools with superior sensitivity and specificity.

The access to bench-stable organometallic compounds unfolds new chemical space for medicinal and material sciences. In particular, stable organoruthenium compounds with constitutional and stereoisomeric forms for subtle regulation of electrochemiluminescence are intriguing and challenging. Here, coordination of polycyclic aromatic hydrocarbons on (2-phenylpyridine)2(CO)2Ru complex allows access to bis-polyaryl phenylpyridine (BPP) Ruthenium complex through C─H activation strategy and coupling reactions for installation of the functionalities with steric and electronic purposes. The photoluminescence and electrochemiluminescence of BPP Ru complexes are affected by the actual polycyclic aromatic hydrocarbons inherent properties. The anthracene derivatized BPP Ru complex (BPP-Ant) shows the best ECL performance and reveals an enormous ECL quantum efficiency of 1.6-fold higher than the golden standard Ru(bpy)3 2+. The unprecedentedly high efficiency is due to the best compromise between the structural conjugation and molecular rigidity from BPP-Ant providing a providential energy gap that facilitated the feasibility of electron transfer and favored the radiative energy release by experimentally and DFT calculations. Moreover, PL and spooling ECL spectroscopies are used to track and link multiple emission peaks of BPP-Ant at 445, 645, and 845 nm to different emissive species. These discoveries will add a new member to the efficient ECL ruthenium complex family and bring more potentials.

Resonance energy transfer (RET) quenching is significantly important for developing electrochemiluminescence (ECL) sensors, but RET platforms face challenges like interference from other fluorescent substances and reliance on energy transfer efficiency. This study used Zn-PTC, formed by zinc ions coordinated with perylene-3,4,9,10-tetracarboxylate, as a dual-mechanism quencher to reduce the ECL intensity of carbon nitride nanosheets (Tg-CNNSs). Co3O4/NiCo2O4 acts as a coreaction promoter, enhancing and stabilizing the luminescence of Tg-CNNSs. Zn-PTC absorbs energy from Tg-CNNSs, altering the fluorescence lifetime to confirm energy transfer, while energy-level matching demonstrates electron transfer. By leveraging both RET and electron transfer mechanisms, the designed ECL aptasensor significantly reduces signal fluctuations that may arise from a single mechanism, resulting in more stable and reliable detection outcomes. The ECL aptasensor designed for furanyl fentanyl (FUF) detection shows excellent performance with a detection limit of 5.7 × 10-15 g/L, offering new pathways for detecting FUF and other small molecules.

The electrochemiluminescence (ECL) effectiveness of the tris(bipyridine) ruthenium(II) (Ru(bpy)32+) system is hampered by aggregation-caused quenching (ACQ) in optoelectronic systems as a result of π-π accumulation of the aromatic ring structure. In this work, a negatively charged tetraphenylvinyl molecule (TPE-2SO3Na, TPE-4SO3Na) was synthesized to modify the electrode interface, and the π-π accumulation between Ru(bpy)32+ molecules was transformed into the π-π interaction between Ru(bpy)32+ and TPE molecules. Interestingly, the ECL signal intensity of the Ru(bpy)32+-tripropylamine (TPA) system in the presence of TPE-2SO3Na was increased by about 15 times due to the π-π action and electrostatic action. In comparison with traditional physical packaging with porous zeolites, metal-organic frameworks (MOFs), and covalent organic frameworks (COFs), the fabricated electrode interface modification strategy was simple and efficient to avoid π-π accumulation in aqueous solutions. Our success will inspire other researchers to investigate the supramolecular interaction (π-π interaction, electrostatic interaction, hydrophilic interaction, and host-guest interaction) at the electrode interface to amplify the ECL intensities of Ru(bpy)32+.

Rapid and sensitive detection for acetamiprid, a kind of widely used neonicotinoid insecticide, is very meaningful for the development of modern agriculture and the protection of human health. Highly stable electrochemiluminescence (ECL) materials are one of the key factors in ECL sensing technology. ECL materials prepared by porous materials (e.g., MOFs) coated with chromophores have been used for ECL sensing detection, but these materials have poor stability because the chromophores escape when they are in aqueous solution. Therefore, the development of highly stable ECL materials is of great significance to improve the sensitivity of ECL sensing technology.

In this work, by combining etched metal-organic frameworks (E-UIO-66-NH2) as carrier with Tris(4,4'-dicarboxylic acid-2,2'-bipyridine)Ru(II) chloride (Ru(dcbpy)32+) as signal probe via amide bonds, highly stable nanocomposites (E-UIO-66-NH2-Ru) with excellent ECL performance were firstly prepared. Then, using MoS2 loaded with AuNPs as substrate material and co-reactant promoter, a signal off-on-off ECL aptamer sensor was prepared for sensitive detection of acetamiprid. Due to the excellent catalytic activity of E-UIO-66-NH2-Ru and MoS2@Au towards K2S2O8, the ECL signals can be enhanced by multiple signal enhancement pathways, the prepared ECL aptamer sensor could achieve sensitive detection of acetamiprid in the linear range of 10-13 to10-7 mol L-1, with the limit of detection (LOD) of 2.78ⅹ10-15 mol L-1 (S/N = 3). After the evaluation of actual sample testing, this sensing platform was proven to be an effective method for the detection of acetamiprid in food and agricultural products.

The E-UIO-66-NH2-Ru prepared by linking Ru(dcbpy)32+ to E-UIO-66-NH2 via amide bonding has very high stability. The synergistic catalytic effect of MoS2 and AuNPs enhanced the ECL signal. By exploring the sensing mechanism and evaluating the actual sample tests, the proposed signal "on-off" ECL sensing strategy was proved to be an effective and excellent ECL sensing method for sensitive and stable detection of acetamiprid.

MicroRNAs (miRNAs) play several crucial roles in the physiological and pathological processes of the human body. They are considered as important biomarkers for the diagnosis of various disorders. Thus, rapid, sensitive, selective, and affordable detection of miRNAs is of great importance. However, the small size, low abundance, and highly similar sequences of miRNAs impose major challenges to their accurate detection in biological samples. In recent years, metal-organic frameworks (MOFs) have been applied as promising sensing materials for the fabrication of different biosensors due to their distinctive characteristics, such as high porosity and surface area, tunable pores, outstanding adsorption affinities, and ease of functionalization. In this review, the applications of MOFs and MOF-derived materials in the fabrication of fluorescence, electrochemical, chemiluminescence, electrochemiluminescent, and photoelectrochemical biosensors for the detection of miRNAs and their detection principle and analytical performance are discussed. This paper attempts to provide readers with a comprehensive knowledge of the fabrication and sensing mechanisms of miRNA detection platforms.

We present a dimensional regulating charge transfer strategy to achieve an enhanced electrochemiluminescence (ECL) by constructing a one-dimensional pyrene-based covalent organic framework (1D-COF). The dual-chain-like edge architecture in 1D-COF facilitates the stabilization of aromatic backbones, the enhancement of electronic conjugations, and the decrease of energy loss. The 1D-COF generates enhanced anodic (92.5-fold) and cathodic (3.2-fold) signals with tripropylamine (TPrA) and K2S2O8 as the anodic and cathodic coreactants, respectively, compared with 2D-COF. The anodic and cathodic ECL efficiencies of 1D-COF are 2.08- and 3.08-fold higher than those of 2D-COF, respectively. According to density functional theory (DFT), the rotational barrier energy (ΔE) of 1D-COF enhances sharply with the increase of dihedral angle, suggesting that the architecture in 1D-COF restrains the intramolecular spin of aromatic chains, which facilitates the decrease of nonradiative transitions and the enhancement of ECL. Furthermore, 1D-COF can be used to construct an ECL biosensor for sensitive detection of dopamine.

Electrochemiluminescence (ECL) as an analytical technology with a perfect combination of electrochemistry and spectroscopy has received considerable attention in bioanalysis due to its high sensitivity and broad dynamic range. Given the selectivity of bio-recognition elements and the high sensitivity of the ECL analysis technique, ECL biosensors are powerful platforms for the sensitive detection of biomarkers, achieving the accurate prognosis and diagnosis of diseases. MicroRNAs (miRNAs) are crucial biomarkers involved in a variety of physiological and pathological processes, whose aberrant expression is often related to serious diseases, especially cancers. ECL biosensors can fulfill the highly sensitive and selective requirements for accurate miRNA detection, prompting this review. The ECL mechanisms are initially introduced and subsequently categorize the ECL biosensors for miRNA detection in terms of the quenching agents. Furthermore, the work highlights the signal amplification strategies for enhancing ECL signal to improve the sensitivity of miRNA detection and finally concludes by looking at the challenges and opportunities in ECL biosensors for miRNA detection.

A multicolor electrochemiluminescence (ECL) biosensor based on a closed bipolar electrode (BPE) array was proposed for the rapid and intuitive analysis of three prostate cancer staging indicators. First, [Irpic-OMe], [Ir(ppy)2(acac)], and [Ru(bpy)3]2+ were applied as blue, green, and red ECL emitters, respectively, whose mixed ECL emission colors covered the whole visible region by varying the applied voltages. Afterward, we designed a simple Mg2+-dependent DNAzyme (MNAzyme)-driven tripedal DNA walker (TD walker) to release three output DNAs. Immediately after, three output DNAs were added to the cathodic reservoirs of the BPE for incubation. After that, we found that the emission colors from the anode of the BPE changed as a driving voltage of 8.0 V was applied, mainly due to changes in the interfacial potential and faradaic currents at the two poles of the BPE. Via optimization of the experimental parameters, cutoff values of such three indicators at different clinical stages could be identified instantly with the naked eye, and standard precision swatches with multiple indicators could be prepared. Finally, in order to precisely determine the prostate cancer stage, the multicolor ECL device was used for clinical analysis, and the resulting images were then compared with standard swatches, laying the way for accurate prostate cancer therapy.

Metal nanoclusters (Me NCs) have become a research hotspot in the field of electrochemiluminescence (ECL) sensing analysis. This is primarily attributed to their excellent luminescent properties and biocompatibility along with their easy synthesis and labeling characteristics. At present, the application of Me NCs in ECL mainly focuses on precious metals, whose high cost, to some extent, limits their widespread application. In this work, Cu NCs with cathode ECL emissions in persulfate (S2O82-) were prepared as signal probes using glutathione as ligands, which exhibited stable luminescence signals and high ECL efficiency. At the same time, CaMnO3 was introduced as a co-reaction promoter to increase the ECL responses of Cu NCs, thereby further expanding their application potential in biochemical analysis. Specifically, the reversible conversion of Mn3+/Mn4+ greatly promoted the generation of sulfate radicals (SO4•-), providing a guarantee for improving the luminescence signals of Cu NCs. Furthermore, a short peptide (NARKFYKGC) was introduced to enable the fixation of antibodies to specific targets, preventing the occupancy of antigen-binding sites (Fab fragments). Therefore, the sensitivity of the biosensor could be significantly enhanced by releasing additional Fab fragments. Considering the approaches discussed above, the constructed biosensor could achieve sensitive detection of CD44 over a broad range (10 fg/mL-100 ng/mL), with an ultralow detection limit of 3.55 fg/mL (S/N = 3), which had valuable implications for the application of nonprecious Me NCs in biosensing analysis.

In this study, a signal-on electrochemiluminescence (ECL) aptasensor for ultrasensitive detection of sulfadimethoxine (SDM) was constructed based on a competitive aptamer strategy. Specifically, cerium-metal-organic framework (Ce-MOF) with large specific surface area and excellent electrical conductivity was combined with gold nanoparticles (AuNPs) to form a substrate, followed by the immobilisation of double-stranded DNA (dsDNA) via AuN bonds. In the presence of SDM, the aptamer tended to form an aptamer-SDM complex, which caused dsDNA to dissociate. After release of the aptamer, the capture probe (CP) combined with the tracer label to enhance the ECL signal. As expected, the prepared sensor displayed an ideal linear response range from 10.0 fg mL-1 to 100 ng mL-1 with a limit of detection (LOD) of 1.28 fg mL-1 and successfully detected SDM in milk and quality control samples.

Nowadays, organic emitters suffer from insufficient electrochemiluminescence (ECL) efficiency in aqueous solutions, and their practical applications are severely restricted in the bio-sensing field. In this work, palladium nanospheres-embedded metal-organic frameworks (Pd@MOFs) were exploited to enhance the ECL efficiency of 2,6-dimethyl-8-(3-carboxyphenyl)4,4'-difluoroboradiazene (BET) prepared by a one-pot method in aqueous environment. First, the Pd@MOFs were generated via in situ reduction of Pd nanospheres anchored onto the MOFs, and fabricated by orderly coordination of palladium chloride (PdCl2) with 1,2,4,5-benzenetetramine (BTA) tetrahydrochloride. Then, the influence of protons on the ECL response of BET was studied in detail to obtain stronger ECL emission using potassium persulfate (K2S2O8) as co-reactant in aqueous environment. As a result, a 1.47-fold ECL efficiency enlargement of BET/K2S2O8 was harvested at the Pd@MOFs/GCE, where Ru(bpy)32+ behaved as a standard. Based on the fact that the ECL signals of the BET-covered Pd@MOFs modified glassy carbon electrode (simplified as BET/Pd@MOFs/GCE) can be quenched by Cu2+, the as-built ECL sensor showed a wide linear range (1.0-100.0 pM) and a limit of detection (LOD) as low as 0.12 pM. Hence, such research offers huge potential to promote the development of organic emitters in ECL biosensors and environmental monitoring.

Most of covalent organic frameworks (COFs) are non or weakly emissive due to either the molecular thermal motion-mediated energy dissipation or the aggregation-caused quenching (ACQ) effect. Herein, we synthesize an imine-linked COF (TFPPy-TPh-COF) with high electrochemiluminescence (ECL) emission and the capability of eliminating the ACQ effect and further construct an ECL sensor for malathion detection. The imine-linked COF is obtained by the condensation reaction of (1,1':3',1″-terphenyl)-4,4″-diamine (TPh) and 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPPy), and it has higher ECL efficiency than TFPPy aggregates due to the separation of ACQ luminophores (i.e., TFPPy) from each other by TPh and the restriction of intramolecular motions of TFPPy and TPh to reduce the nonradiative decay. The efficient quenching of ECL is achieved by electrochemiluminescence resonance energy transfer (ERET) from the excited state of the TFPPy-TPh-COF to zeolite imidazolate framework-8 (ZIF-8) and the steric hindrance of ZIF-8. Acetylcholinesterase (AChE) can enzymatically hydrolyze acetylcholine (ACh) to generate acetic acid. The resultant acetic acid can trigger the dissolution of ZIF-8 to produce an enhanced ECL signal. Malathion as an organophosphorus pesticide serves as an AChE inhibitor to prevent the production of acetic acid, inducing the decrease of ECL signal. This sensor displays a limit of detection (LOD) of 2.44 pg/mL and a wide dynamic detection range of 0.01-1000 ng/mL. Furthermore, it can be used to detect other organophosphates pesticides (e.g., methidathion, chlorpyrifos, and paraoxon) and measure malathion in real samples (i.e., pakchoi, lettuce, and apples).

Nowadays, bacterial resistance caused by the abuse of antibiotics has become a worldwide problem. In this work, a quinolone antibiotic, enrofloxacin (ENR), was rapidly monitored by combining a selective molecular imprinting polymer (MIP) with the electrochemiluminescence (ECL) method. Zn-PTC, a novel zinc-based metal-organic framework (MOF) that has a large specific surface area and ultra-high luminous efficiency, was used as the ECL luminophore. Chitosan (CHIT) was used to contact the specific surface area of molecularly imprinted polymer films and further improved the detection sensitivity. Subsequently, the molecularly imprinted polypyrrole was electropolymerized on the surface of the Zn-PTC and CHIT modified glassy carbon electrode (GCE). The specific sites that could target recombining ENR were shaped on the surface of MIP after extracting the ENR templates. The specific concentrations of ENR could be detected according to the difference in ECL intensity (ΔECL) between the eluting and rebinding of ENR. After optimization, a good linear response of ΔECL and a logarithm of specific ENR concentrations could be obtained in the range of 1.0 × 10-12-1.0 × 10-4 mol L-1, with a detection limit of 9.3 × 10-13 mol L-1 (S/N = 3). Notably, this study provided a rapid, convenient, and cheap method for the detection of ENR in actual samples.

In this study, a novel electrochemiluminescence resonance energy transfer (ECL-RET) immunoassay was developed for the first time for the detection of zearalenone (ZEN). A porphyrin metal-organic framework (PCN-222), an emerging porphyrin-based ECL luminophore, was prepared by a simple hydrothermal method using tetrakis(4-carboxyphenyl) porphyrin, which has excellent ECL emission as well as good ECL efficiency. Because the ECL emission spectrum of PCN-222 is highly matched to the absorption spectrum of gold nanoparticle-modified graphene oxide (AuNPs/NSG) nanocomposites, they were used as donor-acceptor counterparts in this work for the ECL-RET strategy. Under optimal conditions, the ECL immunosensor showed a sensitive response to ZEN in a wide detection range, with a linearity of 0.0005-1000 ng mL-1 and a detection limit of 0.15 pg mL-1. In addition, the sensor showed good potential for application in the detection of wheat and corn samples, providing a new approach for the detection of mycotoxin-like contaminants such as ZEN in food grains.

Various binding modes of tunable metal organic frameworks (MOFs) and functional DNAzymes (Dzs) synergistically catalyze the emergence of abundant functional nanoplatforms. Given their serial variability in formation, structural designability, and functional controllability, Dzs@MOFs tend to be excellent building blocks for the precise "intelligent" manufacture of functional materials. To present a clear outline of this new field, this review systematically summarizes the progress of Dz integration into MOFs (MOFs@Dzs) through different methods, including various surface infiltration, pore encapsulation, covalent binding, and biomimetic mineralization methods. Atomic-level and time-resolved catalytic mechanisms for biosensing and imaging are made possible by the complex interplay of the distinct molecular structure of Dzs@MOF, conformational flexibility, and dynamic regulation of metal ions. Exploiting the precision of DNAzymes, MOFs@Dzs constructed a combined nanotherapy platform to guide intracellular drug synthesis, photodynamic therapy, catalytic therapy, and immunotherapy to enhance gene therapy in different ways, solving the problems of intracellular delivery inefficiency and insufficient supply of cofactors. MOFs@Dzs nanostructures have become excellent candidates for biosensing, bioimaging, amplification delivery, and targeted cancer gene therapy while emphasizing major advancements and seminal endeavors in the fields of biosensing (nucleic acid, protein, enzyme activity, small molecules, and cancer cells), biological imaging, and targeted cancer gene delivery and gene therapy. Overall, based on the results demonstrated to date, we discuss the challenges that the emerging MOFs@Dzs might encounter in practical future applications and briefly look forward to their bright prospects in other fields.

The recognition and separation of chiral isomers are of great importance in both industrial and biological applications. In this study, a chiral recognition system based on electrochemiluminescence was established for the detection of penicillamine (PA) enantiomers. The system utilized a homochiral [Zn2(BDC)(d-lac)] (Zn-BL) platform for the uniform distribution of Ru(bpy)32+ nanoparticles, effectively mitigating aggregation-caused quenching. The chiral recognition ability of Zn-BL was tested to distinguish between PA enantiomers, and the results indicated a substantial increase in the chiral electrochemiluminescence (ECL) signal when l-PA was present, in contrast to d-PA. The mechanism underlying ECL chiral discrimination was investigated using water contact angle measurements, DFT calculations, and electrochemical characterization. The system exhibited high selectivity, stability, and reproducibility for PA enantiomer detection. Furthermore, the proposed method can accurately identify one enantiomer of PA in a mixture. This study provides a reliable and sensitive approach for achieving the highly selective detection of chiral molecules.

The efficiency of aggregation-induced electrochemiluminescence (AIECL) in tetraphenylethene (TPE) derivatives were significantly enhanced by combining the regulation of molecular structure and solvent. Firstly, the linear increase of the benzene ring resulted in enhanced molecular aggregation and promoted the electrochemical reaction of the anode, due to increased molecular conjugation and higher lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO). The ECL efficiency of 4,4,4,4-(Ethene-1,1,2,2-tetrayl) tetrakis (([1,1,4,1-terphenyl]-4-carbaldehyde)) (T3) nanoparticles (NPs) with more benzene rings were 5558 times that of 4,4,4,4-(ethene-1,1,2,2-tetrayl) tetrabenzaldehyde (T1) NPs, and its relative ECL efficiency of T3 NPs reached 55.58% compared to the [Ru (bpy)3]2+/tripropylamine (TPrA) system. Furthermore, solvents with different polarities played a crucial role in modulating the degree of molecular aggregation, which also effectively facilitated the AIE process and reduced the aggregation-caused quenching (ACQ) effect caused by excessively dense aggregation. This aspect had often been overlooked in previous AIECL studies. T3 NPs demonstrated optimal ECL performance at fw = 70% (fw was the H2O content in tetrahydrofuran (THF)/H2O), and its ECL efficiency was 232 times greater than fw = 100% and 1853 times greater than fw = 0%. Additionally, it was found that melatonin (MT), one of the hormones widely used to treat insomnia, exhibited antioxidant and free radical scavenging properties, which exerted a significant quenching effect on the ECL of the T3 NPs/TPrA system. Consequently, a sensitive sensing platform was developed for MT with a low detection limit of 8.78 × 10-10 mol L-1, which promoted the application of AIECL in efficient ultra-sensitive biosensing.

The incorporation of electroactive organic building blocks into coordination polymers (CPs) and metal-organic frameworks (MOFs) offers a promising approach for adding electronic functionalities such as redox activity, electrical conductivity, and luminescence to these materials. The incorporation of perylene moieties into CPs is, in particular, of great interest due to its potential to introduce both luminescence and redox properties. Herein, we present an innovative synthesis method for producing a family of highly crystalline and stable coordination polymers based on perylene-3,4,9,10-tetracarboxylate (PTC) and various transition metals (TMs = Co, Ni, and Zn) with an isostructural framework. The crystal structure of the PTC-TM CPs, obtained through powder X-ray diffraction and Rietveld refinement, provides valuable insights into the composition and organization of the building blocks within the CP. The perylene moieties are arranged in a herringbone pattern, with short distances between adjacent ligands, which contributes to the dense and highly organized framework of the material. The photophysical properties of PTC-Zn were thoroughly studied, revealing the presence of J-aggregation-based and monomer-like emission bands. These bands were experimentally identified, and their behavior was further understood through the use of quantum-chemical calculations. Solid-state cyclic voltammetry experiments on PTC-TMs showed that the perylene redox properties are maintained within the CP framework. This study presents a simple and effective approach for synthesizing highly stable and crystalline perylene-based CPs with tunable optical and electrochemical properties in the solid state.

Improving the electrochemiluminescence (ECL) performance of luminophores is an ongoing research hotspot in the ECL realm. Herein, a high-performance metal-organic framework (MOF)-based ECL material (Ru@Ni₃(HITP)₂, HITP = 2,3,6,7,10,11-hexaiminotriphenylene) with conductivity- and confinement-enhanced ECL was successfully constructed by using conductive MOF Ni₃(HITP)₂ as the carrier to graft Ru(bpydc)₃^4- (H₂bpydc = 2,2'-bipyridine-4,4'-dicarboxylic acid) into the channels of Ni₃(HITP)₂. Compared to Ru@Cu₃(HITP)₂ and Ru@Co₃(HITP)₂ with relatively low conductivity, the ECL intensity of Ru@Ni₃(HITP)₂ was prominently increased about 6.76 times and 18.8 times, respectively, which demonstrated that the increase in conductivity induced the ECL enhancement of the MOF-based ECL materials. What's more, the hydrophobic and porous Ni₃(HITP)₂ can not only effectively enrich the lipophilic tripropylamine (TPrA) coreactants in its channels to enhance the electrochemical oxidation efficiency of TPrA, but also provide a conductive reaction micro-environment to boost the ECL reaction between Ru(bpydc)₃^3- intermediates and TPrA^• in confined spaces, thus realizing a remarkable confinement-enhanced ECL. Considering the excellent ECL performance of Ru@Ni₃(HITP)₂, an ultrasensitive ECL biosensor was prepared based on the Ru@Ni₃(HITP)₂ ECL indicator combining an exonuclease I-aided target cycling amplification strategy for thrombin determination. The constructed ECL biosensor showcased a wide linear range from 1 fM to 1 nM with a low detection limit of 0.62 fM. Overall, the conductivity- and confinement-enhanced ECL based on Ru@Ni₃(HITP)₂ provided effective and feasible strategies to enhance ECL performance, which paved a promising avenue for exploring high-efficient MOF-based ECL materials and thus broadened the application scope of conductive MOFs.

It is essential to develop ultrasensitive biosensors for cancer detection and treatment monitoring. In the development of sensing platforms, metal-organic frameworks (MOFs) have received considerable attention as potential porous crystalline nanostructures. Core-shell MOF nanoparticles (NPs) have shown different diversities, complexities, and biological functionalities, as well as significant electrochemical (EC) properties and potential bio-affinity to aptamers. As a result, the developed core-shell MOF-based aptasensors serve as highly sensitive platforms for sensing cancer biomarkers with an extremely low limit of detection (LOD). This paper aimed to provide an overview of different strategies for improving selectivity, sensitivity, and signal strength of MOF nanostructures. Then, aptamers and aptamers-modified core-shell MOFs were reviewed to address their functionalization and application in biosensing platforms. Additionally, the application of core-shell MOF-assisted EC aptasensors for detection of several tumor antigens such as prostate-specific antigen (PSA), carbohydrate antigen 15-3 (CA15-3), carcinoembryonic antigen (CEA), human epidermal growth factor receptor-2 (HER2), cancer antigen 125 (CA-125), cytokeratin 19 fragment (CYFRA21-1), and other tumor markers were discussed. In conclusion, the present article reviews the advancement of potential biosensing platforms toward the detection of specific cancer biomarkers through the development of core-shell MOFs-based EC aptasensors.

A novel sandwich electrochemiluminescence (ECL) biosensor based on aggregation-induced electrochemiluminescence resonance energy transfer (AIECL-RET) was designed for the sensitive detection of amyloid β42 (Aβ42). The synthesized silver nanoparticle-functionalized zinc metal-organic framework (Ag@ZnPTC) and gold nanoparticle-functionalized zirconium organic framework (Au@UiO-66-NH₂) were used as the ECL donor and acceptor, respectively. AgNPs were generated in situ on the surface of ZnPTC, which further improved the ECL intensity and the loading of antibody 1 (Ab1). Under the optimized experimental conditions, the linear detection range of Aβ42 concentration was 10 fg/mL to 100 ng/mL, and the detection limit was 2.4 fg/mL (S/N = 3). The recoveries of Aβ42 were 99.5-104%. The method has good stability, repeatability, and specificity. Ag@ZnPTC/Au@UiO-66-NH₂ provides an assay for the sensitive detection of disease biomarkers.

The development of electrochemiluminescence (ECL) emitters of different colors with high ECL efficiency (Φ_ECL) is appealing yet challenging for ultrasensitive multiplexed bioassays. Herein, we report the synthesis of highly efficient polymeric carbon nitride (CN) films with fine-tuned ECL emission from blue to green (410, 450, 470, and 525 nm) using the precursor crystallization method. More importantly, naked eye-observable and significantly enhanced ECL emission was achieved, and the cathodic Φ_ECL values were ca. 112, 394, 353, and 251 times those of the aqueous Ru(bpy)₃Cl₂/K₂S₂O₈ reference. Mechanism studies showed that the density of surface-trapped electrons, the associated nonradiative decay pathways, and electron-hole recombination kinetics were crucial factors for the high Φ_ECL of CN. Based on high Φ_ECL and different colors of ECL emission, the wavelength-resolved multiplexing ECL biosensor was constructed to simultaneously detect miRNA-21 and miRNA-141 with superior low detection limits of 0.13 fM and 25.17 aM, respectively. This work provides a facile method to synthesize wavelength-resolved ECL emitters based on metal-free CN polymers with high Φ_ECL for multiplexed bioassays.

Coreactant electrochemiluminescence (ECL) is one of the most popular pathways in commercial analysis, which can provide simplicity and convenience for getting intense ECL emission. However, the low efficiency of intermolecular electron transfer could weaken ECL intensity. In this work, we developed an enhanced ECL strategy through in situ coordination interactions between metal-organic framework emitters and coreactants. First, a metal-organic framework (MOF) emitter was synthesized with 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethane (TPPE) as aggregation-induced emission linkers and Zn as nodes. Interestingly, compared to TPPE ligand, the resulted MOF nanoemitters demonstrated 49.5 folds enhancement of ECL emission in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as the coreactant. More significantly, different from the constant ECL intensity using TPrA coreactant, DABCO exhibited time-dependent ECL intensity due to the intrareticular electron transfer through coordination interaction between DABCO and Zn²⁺, which was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectral experiments. The enhanced ECL was then applied to construct a sensitive ECL method to detect dopamine in serum samples. The coordination interaction between emitters and coreactants not only provides a universal way to enhance ECL, but also expands the applications of coreactant ECL system in convenience route.

In this study, for the first time, a silver-based metal-organic framework (Ag-MOF) was synthesized and used as the electrochemiluminescence (ECL) emitter for building an ECL sensor. After modification with chitosan (CS) and gold nanoparticles (Au NPs), the ECL stability of Ag-MOF was improved. To detect mercury ions, a biosensor was constructed using the mercury ion aptamer and steric effect of streptavidin. First, the capture strand (cDNA) with terminal-modified sulfhydryl group was attached to the electrode surface by the Au-S bond. Then, the mercury-ion aptamer (Apt-Hg) modified with biotin was anchored to the electrode by complementary pairing with cDNA. Streptavidin (SA) could be fixed on the electrode by linking with biotin, thereby reducing the ECL signal. However, in the presence of mercury ions, the aptamer was removed and streptavidin could not be immobilized on the electrode. Hence, the ECL signal of the sensor increased with the concentration of mercury ions, which was linear in the range from 1 μM to 300 fM. The detection limit could reach 66 fM (S/N = 3). The sensor provided a new method for the detection of mercury ions.

The family of electrochemiluminescent luminophores has witnessed quick development since the electrochemiluminescence (ECL) phenomenon of silicon nanoparticles was first reported in 2002. Moreover, these developed ECL nanoemitters have extensively been applied in sensitive detection of protein biomarker by combining with immunological recognition. This review firstly summarized the origin and development of various ECL nanoemitters including inorganic and organic nanomaterials, with an emphasis on metal-organic frameworks (MOFs)-based ECL nanoemitters. Several effective strategies to amplify the ECL response of nanoemitters and improve the sensitivity of immunosensing were discussed. The application of ECL nanoemitters in immunoassay of protein biomarkers for diagnosis of cancers and other diseases, especially lung cancer and heart diseases, was comprehensively presented. The recent development of ECL imaging with the nanoemitters as ECL tags for detection of multiplex protein biomarkers on single cell membrane also attracted attention. Finally, the future opportunities and challenges in the ECL biosensing field were highlighted.

The elimination of aggregation-caused quenching of polycyclic aromatic hydrocarbons by metal-ligand coordination is of immense scientific interest in solid-state electrochemiluminescence (ECL) sensing. Herein potassium ion (K⁺)-mediated J-aggregate K-PTC MOF (PTCA, perylene-3,4,9,10-tetracarboxylic) was synthesized and employed to formulate an ECL immunosensor for biomarker detection. The coordination-driven aggregates are arranged in an end-to-end side mode, which overcomes the aggregation-caused quenching related to PTCA concentration. Compared with PTCA, K-PTC MOF shows a more stable ECL emission with an unprecedented red shift to 718 nm and is equipped with ECL activity for analytical applications at a voltage of -1.1 V. Considering the requirements of accurate detection, metal-phenolic bioactive nanoparticles (MPNPs) were synthesized for the construction of a sandwich sensing platform to realize the steady-state regulation of ECL. As proof of applicability, a constructive experiment was carried out with neuron-specific enolase (NSE), a marker of small cell lung cancer (SCLC), as a targeted analyte. With optimal requirements, the configuration can provide a detection range of 10 pg/mL to 50 ng/mL and a detection limit of 7.4 pg/mL, accompanied by sufficient practical analytical performance. Collectively, this paradigm provides a deeper understanding of the ECL characteristics of coordination-driven J-aggregation and provides more possibilities for the development of ECL patterns based on luminescent metal-organic frameworks.

Developing robust and sensitive food safety detection methods is important for human health. Electrochemiluminescence (ECL) is a powerful analytical technique for complete separation of input source (electricity) and output signal (light), thereby significantly reducing background ECL signal. ECL biosensors have attracted considerable attention owing to their high sensitivity and wide dynamic range in food safety detection. In this review, we introduce the principles of ECL biosensors and common ECL luminophores, as well as the latest applications of ECL biosensors in food analysis. Further, novel nanomaterial assembly strategies have been progressively incorporated into the design of ECL biosensors, and by demonstrating some representative works, we summarize the development status of ECL biosensors in detection of mycotoxins, heavy metal ions, antibiotics, pesticide residues, foodborne pathogens, and other illegal additives. Finally, the current challenges faced by ECL biosensors are outlined and the future directions for advancing ECL research are presented.

In this work, we utilized polycyclic aromatic hydrocarbon (PAH) derivatives as ligands to develop a zinc-based metal-organic framework (Zn-MOF) as an effective detection probe to construct an electrochemiluminescence (ECL) sensor for trenbolone detection. As traditional ECL emitters, PAHs and their derivatives have limited luminescence efficiency because of the aggregation-induced quenching (ACQ) effect. Therefore, Zn-PTC was designed by the coordination of 3,4,9,10-perylenetetracarboxylic (PTC) in the MOF to eliminate the ACQ effect. Meanwhile, Zn-PTC formed based on an aromatic ligand possessed the metal-to-ligand charge-transfer (MLCT) effect, which could transfer the energy of Zn²⁺ to the aromatic ligand for strong luminescence. The ECL efficiency of Zn-PTC was calculated to be approximately 2.2 times that of the ligand (K₄PTC). Second, the Ag@Fe core-shell bimetallic nanocrystal was prepared for efficient activation of persulfate (S₂O₈^2-), thereby generating more sulfate radicals (SO₄^•-) to further promote ECL emission. According to ECL characterizations, UV-vis and fluorescence spectra, and density functional theory calculations, the luminescence and signal amplification mechanisms were investigated. In addition, NKFRGKYKC (NKF) was introduced as an affinity ligand to directionally immobilize the target antibodies, thus releasing specific sites in their Fab fragment to enhance binding activity. Based on the above strategies, the constructed biosensor exhibited high sensitivity, realizing trace detection of TBE with a wide detection range (10 fg/mL-100 ng/mL) and a low detection limit (3.28 fg/mL). This study provided an important reference for sensitive monitoring of steroid pollutants in the environment.

A boron dipyrromethene (BODIPY)-based metal-organic framework (MOF) nanoemitter was for the first time designed with enhanced electrochemiluminescence (ECL) intensity due to the suppression of non-radiative dissipation originating from the ordered arrangement of BODIPY molecules in the framework. Thus, an ECL biosensor was developed for telomerase detection with excellent performance in real samples.

The preparation of highly efficient electrochemiluminescence (ECL) illuminants is an effective method to improve the sensitivity and repeatability of ECL immunoassay. In this study, we prepared an ECL immunoassay for efficient and sensitive detection of neuron-specific enolase (NSE) by linking carboxylated Ru(bpy)₃²⁺ to an iron-based metal-organic framework (NH₂-MIL-88 (Fe)) via an amide bond as an ECL signal probe. NH₂-MIL-88 (Fe) possesses a large number of amino groups that can catalyze the co-reactant S₂O₈^2-, which generates abundant reaction intermediates SO₄^•- around Ru(dcbpy)₃²⁺, reduces the loss of material transport and energy transfer between SO₄^•- and Ru(dcbpy)₃²⁺, and significantly enhances the ECL signal. We used polyaniline-intercalating vanadium oxide (PVO) nanosheets as the substrates to capture NSE owing to the large specific surface area and extraordinary conductivity of the nanosheets. Similarly, PVO nanosheets also possess abundant amino groups, which can act as co-reaction promoters to catalyze the reaction of S₂O₈^2- to SO₄^•-, enhancing the ECL signal of the immunoassay. Therefore, we constructed a dual-enhanced ECL immunoassay with Ru(dcbpy)₃²⁺/NH₂-MIL-88 (Fe) and PVO as the signal probe and substrate, respectively, which exhibited excellent sensitivity and selectivity for detecting NSE. This study offers an effective strategy for ultrasensitive detection of trace proteins using ECL immunoassays.

In this work, a CRISPR/Cas12a initiated switchable ternary electrochemiluminescence (ECL) biosensor combined with a Co3O4@Au nanoemitter is presented for the in vitro monitoring of miRNA-141. Benefiting from the advantages of high-throughput cargo payload capability and superconductivity, three-dimensional reduced graphene oxide (3D-rGO) was designated as an introductory conducting stratum of a paper working electrode (PWE). With the collaborative participation of Co3O4@Au NPs, the transmutation of TPrA in the Ru(bpy)32+/TPrA system can be riotously expedited into exorbitant free radical ions TPrA•, which provoked the exaggeration of the ECL signal. Moreover, the programmable enzyme-free hybrid chain reaction (HCR) amplifier on the PWE surface accurately anchored the assembly of nucleic acid tandem and accomplished the secondary recursion of the signal. Impressively, the multifunctional CRISPR/Cas12a with nonspecific cis/trans-splitting decomposition manipulated the photoswitch of the "on-off" signal state that avoided the false-positive diagnosis. The presented multistrategy cooperative biosensor demonstrated extraordinary sensitivity and specificity, with a low detection limit of 3.3 fM (S/N = 3) in the concentration scope from 10 fM to 100 nM, which fully corresponded to the expectation. Overall, this innovative methodology paved a generous avenue for evaluating multifarious biotransformations and provided a tremendous impetus to the development of real-time diagnosis and clinical detection of other biomarkers.

Porous nanomaterials have attracted much attention in the field of electrochemiluminescence (ECL) analysis research because of their large specific surface area, high porosity, possession of multiple functional groups, and ease of modification. Porous nanomaterials can not only serve as good carriers for loading ECL luminophores to prepare nanomaterials with excellent luminescence properties, but they also have a good electrical conductivity to facilitate charge transfer and substance exchange between electrode surfaces and solutions. In particular, some porous nanomaterials with special functional groups or centered on metals even possess excellent catalytic properties that can enhance the ECL response of the system. ECL composites prepared based on porous nanomaterials have a wide range of applications in the field of ECL biosensors due to their extraordinary ECL response. In this paper, we reviewed recent research advances in various porous nanomaterials commonly used to fabricate ECL biosensors, such as ordered mesoporous silica (OMS), metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and metal-polydopamine frameworks (MPFs). Their applications in the detection of heavy metal ions, small molecules, proteins and nucleic acids are also summarized. The challenges and prospects of constructing ECL biosensors based on porous nanomaterials are further discussed. We hope that this review will provide the reader with a comprehensive understanding of the development of porous nanomaterial-based ECL systems in analytical biosensors and materials science.

Sensitive and accurate detection of nucleic acid biomarkers is critical for early cancer diagnosis, disease monitoring, and clinical treatment. In this study, we developed a switch fluorescence biosensor for simple and high-efficient detection of nucleic acid biomarkers using 6-carboxyfluorescein (FAM)-modified single-stranded DNA (ssDNA) probes (FAM-P1/P2), and zirconium porphyrin metal-organic framework nanoparticles (ZrMOF) acted as fluorescence quencher. FAM-P1/P2 probes were adsorbed on ZrMOF surface because of π-π stacking, hydrogen bonding, and electrostatic interactions. Fluorescence quenching event occurred by fluorescence resonance energy transfer (FRET) and photo-induced electron transfer (PET) processes, thereby achieving the "off" fluorescence status. Once the specific binding was formed between the fluorescence probes and the targets, the rigid double-stranded DNA (dsDNA) structures were released from ZrMOF surface, resulting in the recovery of fluorescence and the "on" status. Because of the superior adsorption ability of ZrMOF toward ssDNA than dsDNA, the switch of fluorescence signals from "off" to "on" allowed rapid and ultrasensitive detection of ssDNA (T1) and microRNA-21 (miR-21) within 30 min. The limit of detection (signal-to-noise ratio = 3) for T1 and miR-21 were 2 fM and 11 aM, respectively. Moreover, the proposed strategy was very simple as it worked by the facile adsorption-quenching-recovery mechanism without difficult and complicated immobilization processes. Also, this biosensor showed an excellent analytical performance in the detection of miR-21 in human serum samples. Therefore, this biosensor might be considered a potential tool for the detection of DNA and miRNA biomarkers in clinical samples.